Fluoride containing compositions for removal of pollutants from waste waters and methods of utilizing same

ABSTRACT

Novel compositions containing fluoride are provided for the removal of organic and heavy metal pollutants from waste waters and methods of utilizing same. The compositions comprise components selected from ion exchange absorbent gels, cements, water soluble fluoride containing salts and optionally alkali metal ortho phosphates. The procedures of the present invention yield not only clarified waters but provided a sludge which can be disposed of under environmentally acceptable conditions.

This application is a division of application Ser. No. 424,902, filedSept. 27, 1982, now U.S. Pat. No. 4,436,645.

BACKGROUND OF THE INVENTION

Much attention has been given in recent years to the purification ofwaste waters containing environmentally damaging pollutants such asheavy metals and organic compounds such as found in petroleum wastes. Inorder to return such waste waters into the environment it is necessaryto remove the pollutants in order to reduce environmental contamination.Acceptable methods of treatment include procedures which not only reducethe pollutant level of the treated waters to an environmentallyacceptable standard but also to provide a means of disposing of theremoved pollutant materials in a manner which would not of itselfthereafter contaminate the environment.

Many procedures are known, however, the most efficient of theseprocedures involve the use of expensive, substantially containuous plantinstallations. A need therefore exists for procedures involvingrelatively inexpensive treatment compositions which can be adapted notonly for continuous use but for batch use as well. Ideally such materialshould yield a product which is relatively easily dewaterable and whichhas very low environmental leach characteristics.

The current standards for non-hazardous solid waste in drinking waterare found in the U.S. Environmental Protection Agency publication: EPSW846 "Test Methods for Evaluating such wastes" Section 7: Extractionprocedure, Toxicity Section 7.1-3; Structural Integrity procedureSection 7.1-8.

SUMMARY OF THE INVENTION

The present invention comprises the provision of a novel multi-componentcomposition which will very rapidly remove heavy metal, organic, orpetroleum based pollutants from waste waters and which will provide aresidue which meets environmental disposal standards.

The compositions of the present invention comprise three groups ofcomponents and optionally a fourth. The primary group comprises ionexchange absorbent gels consisting of at least one member of the groupof Clays, preferably calcined clays, silicas, suitably amorphoussilicas, such as diatomaceous earths, aluminas, natural or artificialzeolites, perlites or vermiculite. The second group comprisescementitious materials such as cements, for example, Portland, aluminousand puzzalan cements, gypsum plaster, and alkaline earth metal oxidessuitably hydrated oxides. The third component comprises water solublefluoride salts the optionally component comprises alkali metal orthophosphates. While, under certain circumstances, the presence of thephosphate is not critical, and the compositions are operative withoutit, its presence substantially enchances the efficiency of the system.

In carrying out the process of the present invention, the pollutedwaters are contacted with the treatment compositions in a ratio ofcomposition to pollutant in the range of 5:1 through 25:1.

The water clean-up step is virtually instantanious. It has been found,however, that for environmentally acceptable disposal of the residue,namely the product of the treating composition and the pollutant, asetting time is desirable. While no minimum setting time has beendetermined it has been found that a setting time of 24 hours is adequateto meet Environmental Protection Agency leaching standards. In carryingout the procedures of the present invention, the cure of the residue maybe effected by leaving the residue in contact with the purified watersfor 24 hours or by separating the major portion of the purified waters,allowing the residue to cure and thereafter dewatering same prior todisposal of the residue. No difference in the environmentalacceptability of the residue has been found.

DESCRIPTION OF THE PREFERRED EMBODIMENTS

The present invention is particularly concerned with the treatment ofwaste waters which contain as pollutants the following types ofmaterials.

(1) heavy metals, i.e. copper, chromium, zinc, lead, molybdenum,tungsten, manganese, iron, cobalt, mercury, arsenic, nickel and titaniumions;

(2) organic water-miscible substances, such as phenols, i.e., catecholor stearates.

(3) organic water-immiscible substances which form emulsions or slickswith water, i.e. petroleum distillates and

(4) water soluble inorganic ions, such as cyanide.

The compositions which are utilized in the present invention comprisemixtures of at least three components selected from the following groupsof components:

(a) ion exchanging absorbent gels. This group includes clays mostsuitably calcined clays, silicas suitably amorphous silica such asdiatomaceous earths, alminas, natural and synthetic zeolites, perlite orvermiculite. These materials may comprise between 15 and 55% by weightof the total compositions.

(b) cementitious materials such as cements, including portland,aluminous, and puzzalan cements, gypsum plaster, alkaline earth metaloxides or alkaline earth metal hydrated oxides. This group may comprisebetween 30 and 80% of the mixture.

(c) water soluble fluoride containing salts most suitably ammoniumbifluoride (NH₄.HF₂), zinc fluorosilicate (Zn) SiF₆, magnesiumfluorosilicate (MgSiF₆), zinc fluoro borate (³ ZnF₂.² B₂ O₃) andpotassium fluoride (KF) and stannoulfluoride (SnF₂) may be particularlymentioned but should not be considered as exclusive and

(d) alkali ortho phosphates most preferably sodium ortho phosphate.

It is not critical that phosphates be included for the compositions tobe operative, however, where up to 20% of the total weight of thecomposition of phosphate is present the efficiency of the process issubstantially improved.

It is required within the scope of the present invention that thecomposition contain a source of fluoride ions, and, where no phosphateis present either clay, or a further group (b) component, preferablybetween 20 and 30% by weight is required.

As the cementitious component there may be employed either a cement or agypsum, however, this should be supplemented by a fourth component takenfrom either group (a) for example, diatomaceous silica or from thecementitious group, (b) for example, hydrated lime, in each it ispreferred that this fouth component be present in the same proportion(approximately) as the clay component.

Where no phosphate and no group (a) components are present threecomponents may be selected from group b. In this case at least two ofthree components should be cementitious materials which also have ionexchanging properties such as cements or gypsum.

In carrying out the process of the present invention it is desirable tohave an approximate idea of the pollutant proportion. The amount oftreatment composition utilized should lie between 5 parts of treatmentcomposition to one of pollutant through to 25 parts of treatmentcomposition to one part of pollutant. The higher proportions should beutilized either where very low heavy metal residues in the clarifyingwaters are required or else where the organic pollutants have dyequalities. In carrying out the process of the present invention thecomponents are mixed at ambient temperature. Removal of heavy metals issubstantially instantaneous, while removal of organics may require up to72 contact hours although in most circumtances 24 hours of contact issufficient. At the option of the operator the clarified waters may beseparated from the residue but the residue should be permitted to curefor at least 24 hours prior to dewatering and disposal.

EXAMPLE 1

To an artificial waste water containing 4000 ppm chromium ion, 1600 ppmcopper ion and 3,300 ppm catechol is added, with stirring, a treatmentcomposition containing

37.0 grams Portland cement

28.0 grams Clay (bentonite)

28.0 grams diatomaceous silica

7.0 grams zinc fluorosilicate

After allowing the artificial waste water and treatment composition tostand for 48-72 hours, the water and sludge are separated. The clarifiedwater was found to contain 0.8 ppm chromium ion, less than 2 ppm copperion and less than 2 ppm of catechol. The sludge is found to be resistantto the E.P.A. leaching test EPSW 846: Extraction Procedure ToxicityReaction 7.1-3.

EXAMPLE 2

One thousand milliters of potable water and 11.78 grams of crystalcopper sulfate are mixed to provide a "waste water" containing 2,000 ppmcopper. To this "waste water" solution is added, with stirring, atreatment composition containing

15.60 grams Portland cement

23.60 grams Calcined Georgia clay

10.0 grams trisodium phosphate

0.8 grams magnesium fluorosilicate

The "waste water" is allowed to stand for 48-72 hours with the treatmentcomposition. Then, the water is separated from the sludge. Both aretested to determine copper content. The clarified water was found tocontain 2.8 ppm copper. The E.P.A. extracted sludge released 3.7 ppmcopper.

EXAMPLE 3

In 3,340 milliliters potable water, there is dissolved 60.0 grams coppersulfate crystals, 0.1 gram fluoroescent tracer dye, 1.0 gram alkyl arylsulfonate wetting agent, 90.0 grams sodium chloride, 30.0 grams chromealum crystals and 10.0 grams catechol to form an artificial waste. Thesolution, a dark foamy solution with considerable phenol odor, isallowed to stand 48 hours and is then treated for 48-72 hours with atreatment composition containing

53.4 grams Portland cement

80.8 grams Calcined clay

30.0 grams trisodium phosphate

5.3 grams ammonium bifluoride

After treatment, the water is separated from the sludge. Both are testedto determine their pollutant content. The clarified water was found tocontain 4.2 ppm copper, 2.5 ppm phenol and 0.14 ppm chromium. The E.P.A.extracted sludge released 3.5 ppm copper, 1.3 ppm phenol and 0.0 ppmchromium.

EXAMPLE 4

In 1000.0 ml potable water is dissolved 20.0 gram chrome alum crystalsso as to provide a "waste water" containing 2,000 ppm Chromium. To this"waste water" is added, with stirring, a treatment compositioncontaining

23.4 grams Portland cement

35.4 grams Amorphous silica

10.0 grams trisodium phosphate

1.2 grams sodium bifluoride

After treatment for 48-72 hours, the water is separated from the sludge.Both are tested to determine chrome content. The clarified water wasfound to contain 0.8 ppm chrome. The E.P.A. extracted sludge released0.93 ppm chrome.

EXAMPLE 5

Two hundred pounds water, 200 pounds petroleum distillate (boilingpoint, 270° C.), 5.0 pounds nonionic wetting agent Igepal Co530 and 0.2pounds is emulsied with high speed stirring to form a stable emulsion of"artificial water". To this is added, with slow speed stirring, atreatment composition containing

320.0 pounds gypsum plaster

40.0 pounds calcined clay

40.0 pounds hydrated lime

2.0 pounds ammonium bifluoride

This produced a smooth easy-flowing paste that was dumped and set in 30minutes a hard, rock-like consistency. This product passes the E.P.A.Structural integrity test and when extracted releases less than 1% ofthe petroleum distillate.

EXAMPLE 6

Two hundred pounds water, 200 pounds petroleum distillate (boilingpoint, 270° C.), 5.0 pounds nonionic wetting agent Igepal Co530 and 0.2pounds is emulsied with high speed stirring to form a stable emulsion of"artificial water". To this is added, with slow speed stirring, atreatment composition containing

16.0 pounds gypsum plaster

16.0 pounds portland cement

8.0 pounds hydrated lime

4.0 pounds magnesium fluoro silicate

This produced a smooth easy-flowing paste that was dumped and set in 30minutes a hard, rock-like consistency. This product passes the E.P.A.Structural integrity test and when extracted releases less than 1% ofthe petroleum distillate.

EXAMPLE 7

Repetition of each of the foregoing Examples 2 through 5 without thefluoride salt results in sludge products which upon E.P.A. extraction,released from 100 to 500 times the amount of toxin as did thecorresponding example containing the fluoride salt.

I claim:
 1. A method for the removal of pollutants from waste waterwhich comprises contacting the waste waters to be treated with acomposition comprisingat least members of groups (b) and (c) of thefollowing groups (a), (b), (c) and (d): (a) ion exchange absorbent gels,consisting of at least one member selected from the group consisting ofcalcined clays, amorphous silicas, aluminas, natural and artificialzeolites, perlites or vermiculite, (b) cementitious materials selectedfrom the group consisting of Portland cements, aluminous cements,puzzalan cements, gypsum plasters, alkaline earth metal oxides andalkaline earth metals hydrated oxides, (c) water soluble fluoridecontaining salts, and (d) alkali metal ortho phosphates, provided thatwhere no alkali metal ortho phosphate is present an additional componentis selected from the group (a) or group (b), further provided that whereno alkali metal ortho phosphate or group (a) components are present,three components are selected from group (b), at a pH above pH 6.0 andallowing the sludge formed thereby to cure for at least 24 hours.
 2. Amethod according to claim 1 wherein the absorbent gels of group (a)comprise between 15 and 55 parts by weight of the total composition, thecementitious materials of group (b) comprise between 30 and 80% byweight of the total composition, the fluoride containing salts comprisebetween 0.2 and 10% by weight of the total composition and the alkalimetal ortho phosphate comprises between 0 and 20% by weight of the totalcomposition provided that where no phosphate is present the fourthcomponent is selected from group (a) or group (b) and comprisessubstantially the same proportion of the total composition as theinitial component selected from group (a).
 3. A method according toclaim 2 wherein the sludge is separated from the clarified water andthen allowed to cure.
 4. A method according to claim 2 wherein thesludge is allowed to pure prior to separation from the clarified water.5. A method according to claim 2 wherein the ratio of treatmentcomposition to pollutant is in the range of 5 to 1 through 25 to
 1. 6. Amethod according to claim 1 wherein the sludge is separated from theclarified water and then allowed to cure.
 7. A method according to claim1 wherein the sludge is allowed to cure prior to separation from theclarified water.
 8. A method according to claim 1 wherein the ratio oftreatment composition to pollutant is in the range of 5 to 1 through 25to
 1. 9. A method of removing the pollution from waste water andproviding a solidification cement, said cement being substantiallyunleachable with respect to said pollutant which comprises contactingthe waste waters to be treated with a composition comprisingat leastmembers of groups (b) and (c) of the following groups (a), (b), (c) and(d): (a) ion exchange absorbent gels, consisting of at least one memberselected from the group consisting of calcined clays; amorphous silicas,aluminas, natural and artificial ziolites, perlites or vermiculite, (b)cementitious materials selected from the group consisting of Portlandcements, aluminous cements, puzzalan cements, gypsum plasters, alkalineearth metal oxides and alkaline earth metals hydrated oxides, (c) watersoluble fluoride containing salts, and (d) alkali metal orthophosphates, provided that where no alkali metal ortho phosphate ispresent an additional component is selected from the group (a) or group(b), further comprising that where no alkali metal ortho phosphate orgroup (a) components are present, three components are selected fromgroup (b).
 10. A method of claim 7 of removing pollution from wastewater and providing a solidification cement, said cement beingsubstantially unleachable with respect to said pollutant which comprisescontacting the waste waters to be treated with a composition comprisingno group (a) components, three materials of group (b) comprising between90 and 99.7% by weight of the total composition, the fluoride containingsalts comprise between 0.3 and 10% by weight of the total compositionand comprising no alkali metal ortho phosphate.
 11. A method of claim 10wherein the composition comprises substantially75% gypsum 19% 50:50mixture calcified clay and lime; and 0.4% ammonium bifluoride.
 12. Amethod of claim 10 wherein the composition comprises substantially37%Portland cement; 28% bentonite clay; 28% diatomaceous silica; and 7%zinc fluorosilicate.